Process of concentrating ores by selective froth flotation



United States Patent PROCESS OF CONCENTRATING ()RES BY SELECTIVE FROTH FLOTATlON Edward H. Snyder, In, Salt Lake City, Utah No Drawing. Application March 2, 1953 Serial N0. 339,941

8 Claims. (Cl. 209- 166) This invention relates to processes of ore concentration by sel'e'c'tive "froth flotation utilizing certain chemical reagen ta andis especially usefulas applied to ores not here- 'tofore r'e'atlilyfloated, particularly the so-called oxidized metallic and submetallic ores.

While -the' process :of the invention has outstanding utillty in connection with these difficult to float ores, and achi'eves an unusually effective and economical beneficia- 'tion ther'eof, leading'to eflicient recovery of the metallic and sub'me'tallic values .contained thereby, its usefulness 'is :uot'restricted to ores of this character. I have found that the processzmay be applied successfully to what are generally regarded as nonmetallic ores, where the mineral valuesto be recovered contain no heavy metallic component, for example, a fluoritic ore whose valued mineral compouent is :fluorite (CaF Furthermore, while its use: is notgenerally indicated in instances of sulfide ores, which are adequately handledby conventional processes "and reagents, the process of the invention is at least operable withrespect thereto, and may consequently be re- ;garded as a process of general applicability in the flotation art, subject, of course, to the usual considerations of relative -economics-in instances .of particular ores.

Theinvention involves the use, .in connection with a difierential froth. flotation procedure, of a reagent belong- 1 ing to a class new to the flotation art. In some-instances, the' reagents employed are new products from a chemical standpoinh'eventhough conforming to a known broad class of generally applicable chemical compounds.

Certainforms ofthe new class of reagents are especially applicable to particular situations as against other forms, for'example, one form has proven selective with respect to the carbonate minerals as against thenoxide min- -erals,and such.forrn may be utilized, for example, to selectively float ofi the lime constituent of an oxide ore having a high lime content from a flotation pulp of such ore, While another form maybe-employed in a subsequent flotation operation on the de-limed residual ore pulp to selectively recover the valued oxide imineral. component thereof.

The-new class of reagents conforming tozthis invention embodies.thephosphines, bothinorganicaud organic, and -:the-hydrides of phosphorous generally, whether occurring in the: gaseous, liquid, or-solid state.

-One of.themost 'useful.members oftthe classfrom the standpoint uof reagent preparation. .is the inorganic phosphine (PH which is normally a gas. While the gas "maylbe introduced directly into the'ore pulp,'ormay be l produced therein in several different ways, e. g. by introduc'tion of ametallic-pho'sphide, such astr-i-calciumdi- 1 phosphide {Ca-4P to the aqueous pulp; yielding PH -as a decompositionproduct,or by introduction-of a phosphonium halide (PHQX) which also yields PI-l as a decomposition product, I'prefer to first intermix'thegaseous PHg with an organic liquid, and .toutilizefthe result- =ingproductas a dire'ct'ad'dition to the ore pulp, either in the"gritiding circuit; conditioner, "or fl'ot'ation" circuit.

A liquid which I have found to be particularly well suited as a vehicle for the phosphine gas in the production of an effective flotation reagent is ordinary kerosene. This reagent maybe easily made by pouring a quantity of kerosene upon a body of water in an open vessel, and by dropping a number of pieces of tricalcium diphosphide through the layer of kerosene into the body of water. i hosphine gas will be evolved as the calcium phosphide hydrolyzes, and, rising through the kerosene, will be absorbed thereby. The kerosenemay then be decanted for use, or the entire body of liquid may be made into an emulsion and used in that form.

Alcohols also serve as effective agents for intermixture with the'phosphinegas in the preparation of reagents suit able for purposes of the invention. Thus, calcium phosphide may beintroducedinto amyl alcohol audwater in a mannerwsimilar to that described above for kerosene, and used as a straight alcohol solution or as an emulsion.

In both of the above instances, the preferred proportions of the respective ingredients are fifty percent each of the liquids, by volume, and calcium phosphide in the amount of one and oneahalf percent of the weight of the combined liquids.

Another form of .the reagent is prepared by reactingcalcium phosphide with an aqueous solution of the proprietary reagent productbearing the name Emcol 4150 produced .by Emulsol Corporation. This product is a sulfate "ester of .alcohols containingeight to ten carbon atoms, and, for purposes of this invention, is made up in preferably a five percent (,by weight) aqueous solution prior to the addition of the phosphi-de in amount equivalent to five tenths of one percent of the weight of the solution.

All of the ,abovereagents requirefrom eightto twelve hours for preparation andare preferably stirred intermittently during such time.

A variety of other useful reagents may be-made up for application in accordance with the invention. Thus, oleic acid may be included as an additional reactant in the preparation of the above reagents, resulting in complex organic compounds exhibiting additional useful qualities in the flotation process.

A sulphonated cresylicacid reagent of phosphinic character has been prepared by mixing cresylic acid by volume) with concentrated sulfuric acid (25% by volume), and diluting the resulting solution by addition of fifty percent of its volume of water. Approximately three grams of calcium phosphide was ,reacted with one hundred cubicv centimeters of thedilute solution for a period of from twenty to twenty-four hours, with intermittent stirring. Both solid and liquid reaction products were produced,:and were found to be satisfactory when used .either separatelyor together as reagents in the flotation process.

Calcium phosphideihas beensuccessfully reacted with a mixture of benzyl chloride and'water to produce another reagentconforming tQ the-general class concerned. Thus,

three grams of calcium-phosphidewas added to one hundred cubic centimeters of a solution made up of-equal parts by volume of benzyl chloride and Water. The reaction wasallowed to proceed for from thirty-six tofortyeight'hours, 'with intermittent agitation. Here, however,

' noxious fumes were produced, so care had to be exercised.

'solid hydridemay be introduced directly into, the ore pulp,

- ly rendering With respect to the gaseous phosphine (PH it might be noted that in addition to the several ways of producing it mentioned hereinbeforaan acid such as hypophosphorous acid will decompose when added to a flotation pulp, yielding PHg, and elemental phosphorous will react with an alkali in the pulp to also make PH available for the purposes of the invention. While these are not preferred methods of introducing the reagent in an ore pulp, they are mentioned herein as possibilities line with the general inventive concepts.

Any process of selective froth flotation involves the generation of numerous and persistent air bubbleswithin an aqueous pulp containing mixed particles of values and so-called gangue or waste. The bubbles rise to the surface as a froth, carrying along material particles which have selectively become attached thereto. Removal 'of the resulting material-bearing froth eifects a separation ,of

. those material particles which have become attached to the bubbles, from those which have not.

It is a principal purpose of the flotation process, therefore, to so treat the ore pulp as to-insure as clean a separation as possible between the Wanted particles and those that are not wanted.

As one aspect of the process, it is necessary that there be present in the ore pulp an agent capable of selectivecertain of the particles amendable to bubble attachment. Such an agent is generally termed a collector or promoter, and normally consists of a hydrocarbon, or contains a hydrocarbon as an essential part thereof.- r

Often it is advisable that the finely divided ore be treated by other agents, to render certain components thereof reactive to the collector or promoter, or more reactive than would otherwise be true. 'These agents are generally termed activators or modifiers. If, however, the reverse condition be desired, namely, the rendering of certain normally reactive components of the ore non-reactive to the collector or promoter, so that they will not float, an agent capable of accomplishing this result is added. Such an agent is generally called a depressant, I

'The process of the present invention, in its various phases as hereinafter set forth, is concerned with all of these aspects of the flotation art.

Thus, I have found that a reagent conforming to the general class of compounds set forth hereinbefore, applied to an ore pulp either by a conditioning treatment in advance of the flotation operation, or accompanying other reagents during the flotation operation, serves as an activator or modifier with respect to many minerals not heretofore considered susceptible of separation from gangue constituents of their ores by the froth flotation process, or heretofore floated only with difliculty. Furthermore, I have found that such a reagent'has adecided and beneficial depressing action in some instances, notably. on certaincompounds of iron, as iron oxides, and on particles stained by iron.

In the froth flotation of sulfide minerals from their ores, or of oxide minerals which have their surfaces effectively altered to an ecca-sulfide (sulfidized) state by appropriate chemical treatment with a suitable activator or modifier, a great variety of chemical vreagents have been found to exhibit marked-collecting or promoting properties for the valued minerals as against gangue. The, most practical ,andthe most widely used of these reagents belong to'a class known as sulphydric, of which the Xanthates are the principal members. Thus, for example, in his Handbook of Mineral Dressing, page 12-07, Arthur F. Taggart citesvas collectors or promoters certain organic sulphydric compounds having a type for-1 mula X-SH, in which X is any one of a'great variety of'loadings containing hydrocarbon groups.

In these compounds, or their corresponding salts, the reactive bond S determines capacity for filming surfaces of the mineral particles, whether acting throughphysical adsorption or chemical replacement of H or of the alkali ion, while the hydrocarbon group provides the film which gives to such mineral particles a hydrophobic or water repellant character and thereby determines their adherability to the flif-WalIBI' interface of the bubbl s, and, consequently, their attachment to and their floating with the bubbles in the froth, selectively with respect to'the gangue materials present in thesore pulp.

Thus, it maybe said that the sulphur component .of these sulphydric collectors determines their preferential affinity for the sulfide particles of the ore, or for other,

particles which have been eflectively. altered to an eccasulfide conditionby appropriate activation treatment.

In accordance with the present invention, however-, it appears that phosphorous provides the reactive bond be tween the desired mineral'particles and the hydrocarbon,

and that various mineral surfaces may be phosphidized -in a manner analogous to sulfidization, being thereby rendered amendable to collection or promotion in much pulp by customarysulfide flotation the same way as in sulfidefflotation. Collectors used in conjunction with such activated or modified minerals may. be either of the anionic or cationic type, but the former generally give more satisfactory results and are ordinarily preferred. It might be said, furthermore, that sulphydric collectors are not normally indicated for use with the process of the invention, this being obvious from the above discussion.

In some instances, the success of the invention may be due to the cleansing of the mineral surfaces by reason of the 'strongreducing action of phosphine. Regardless of what phenomenon is involved, however, practice of the invention is productive of unique and highly useful results, as will be apparent from the examples of actual tests detailed below. a v

While, ordinarily, the reagentsjof the invention are best employed as activators or as so-called collector-modifiers in association with other conventional reagentsof collector or promoter type, there are instances where the organic reaction products of phosphine gas, or of the other phosphorous hydrides, and the organic phosphines have sufiicient collecting or promoting action in themselves to effect recovery without the addition of conventional collectors.

Following are several typical examples of'the process of the invention applied to a variety of different ores, many of which have not heretofore beensusceptibleyof economical treatment by froth flotation: r

v Example N0. 1

The ore treated was an oxide manganese type"fi'om the Caselton properties of Combined Metals Reduction Comp-any in the Pioche District of Nevada. Thisore is composed largely of the manganese minerals psil omelane, H (Ba, Mn, Mg, Ca) M11 02), and manganite, MnO(OH). The gangue minerals are quartz,iron oxides, clay,-calcite, and mica. Minor quantities of sulfides are present in the form 'of pyrite, s phalerite,-and galena. i g

Since the reagentsof the invenfionare. not ordinarily selective as between the oxidized minerals and the sulfides, the sulfide mineralswere first removed from .the ore v procedures. The'pulp residue, or tailings, from this operation were then subjected to flotation procedures in accordance with this invention as indicatedbelow, it being noted that the kerosene phosphine reagent described above was employed in a preliminary conditioning operation as well as in the subsequent flotation, together with conventional carboxyl collectors. This was a series test. 7 i

hereinbefore, the fletatignpfithe- Reagenta Candi-.5 Rougher Cleaner cleaner; Cleanen ing carriedoutasfollowsz. (Lb/Ton). .tloner. A B C Sodimnfiilicate--. 1.3v 0.25 0.25 Nothing. Reagent. .QQEQ17...R9BE11QI 0102mm Cleaner. Cleaner SodiumCar-bonate. 4.5 W (Lb/Ton) tioner A B C sodiumfiyaniden 0.4 0.13 w Kerosene Phos- 5.3 0.5 1.0

phlne Reagent. Sodium Silicate-.- 2.0. Nothing, OleicAcid 2.9m 1.0 0.7' 1.0 Sodium Carbonate. 10.0 Sodium O 0.07. 0.07 0.07 0.07 Sodium Cyanide. 0.5 PH, 9.'6' :mln-

10 min- 12min- 1 O utes utes, utes Sulfonated Cresylic Acid Phos- Gees-.1- 2-2 3-1 3-1 .1 I 80 0 The followmg. results were obtained. Kern m L6 0:2 0'2 PH v 9,;

Percent Assay Percent Distri- 15 2%? Percent bution I Product Weight a v I .Iron 'l'n sol. Mang., .Iron. .Mang.

Concenw- .e b ed mean.-. 52.0 9.5 0.4 33.1 0723. 73.0 0. M 385 .fifi 18 1. Telling 47.4 17.7 38.5 13.5 02.7 27.0 oalmflatgd .P.-. H v ercentAssay- Percent Distri- Head 100.0 13.4 23.3 23.8 100.0 100.0 lemma. bulfionyl rodu t ..We.. v. ExampleNaZ Iron-r Insol- M ne; n-.1 ane.-

The same ore was treated in a similar manner, but em.- ploying an organic phosphine, namely, triphenyl phos- Miglganese a 11cm. phine (PhgP), as the reagent of the lnventlon. The proce- 5 ,0 35.5 15.2 32.7 durem float ng the manganese mmerals was as follows: 5.3 122736; 20b4, 2868 6.7 as Reagent Condi- Rougher. Cleaner Clcaner Cleaner 1559" 2559 243 2242 Al 0 21:8 15.7 45:6 15.95; 32.0 19.0 :15. 5.15; 7.2.; 20.5. 16;2 Sodium Carbonate. 8.0 calculated gggfi g gggfga-r g-g f Head 100.0 1 50.0 17.7 100.0 100.0

utes Tripheuyl Phos hine 0. 4s 0. 1 0. 05. 01el c Ac1d 0.3 0.5 0.5 40 Kerosen 1.7 ."0.3 0.3 pFI 9.5 Egamplefla} utes The same ore was subjected to similar batchprocess ng The resultswere as follows: utilizingithe .benzyl chloride phosph ne reagent.described Percent Assay Percent Dlstri Percent bution Product Weight 1 Iron 111501 ,Lime Mang. Iron Mang.

Manganese C0ncen-..

m 49.0 8.0 11.2 9.6 20.45 39.0 70.1 51. 0 12.9 53. 4 Tr. 10. 30 61. 0 29.9 Calculated Head 100.0 '32.7 10.8 4.7 isT-E 100.0 100.0

Inthis instance the reagent of the invention-was utilized n yinth fl at on-pha of the p ra i nfo i ustr purposes. It is to be understood that it could just'as well have been employed in the conditioning stage as in Example No. 1. In fact, it is preferred in pliactice to pond} fion pr o to he o ion per t in-o en toreduce .Ihe flotation time. 1

x mple. No. 3 a

The same ore was subjected to batch treatment utilizing the sulfonated cresylic acid phosphine reagent described 76 hereinbefore, the manganese flotation being carried out m"aliasesissiewasabiaiea. I j {1 'f Percent Assay Percent Distrl- Percent button Product Weight Iron Insol Mang. Iron .lMang.

Manganese Concen trates 14. 3 15. 9 l2. 36. 45 20. 6 29. 9 Cleaner Teiling C 4.7 14. 55 20. 1 30. 60 0.2 S. 2 Cleaner Tailing B 15.2 16.70 I 21.0 27.65 23.4 24.2 Cleaner Tail- H...

in; A 20.5 12.70 43.8 17.05 23.7 20.0 Talling 45.3 6.30 72.2 6.80 26.1 .17.?

Calculated Herman..." 100. 0 11. 0 47. 7 17. 100. 0 100. 0

It should be noted that the oxidized manganese ore treated in the above examples had theretofore never been satisfactorily floated,.see U. S Burea u of MinesfReport of Investigations No. 4111 ofAugust 1947 entitled Concentration of Manganese Cres from Lincoln- County, Nev., particularly pages-4 and 5, where the particular ore corresponding to that of the foregoing ex'amples is the highly oxidized Zero Gap variety. The results obtained by the tests indicate that this ore can be profitably treated incommercial operations based upon the process of this invention.

The depression of iron by the reagents of the invention is well indicated by the foregoing examples. This features of the invention is, however, shown more significantly in connection with an ore embodying a greater proportion of the iron component relative to the other ore constituents. The following example is directed particularly to this aspect of the invention. Example N o. 5

The ore was 'an oxidemanganese type from the Comet District of Nevada. As in the preceding examples, psilomelane and manganite are present as principal manganese minerals. Another principal manganese mineral in the present instance is pyrolusite, MnO- Iron oxides make up the major portion of the gangne constituents. only minor portions of quartz andothersilicates being present The batch procedure followed in this test was as follows:

Reagent (Lb./Ton) Ball Mill Rougher Cleaner A Cleaner B Sodium Carbonate--. Sodium Silicate Nothing. Sodium Cyanide..- Kerosene Phosphine Reagent.

Oleic Acid DH- The following results were obtained:

Percent Assay Percent Distri- Percent bution Product Weight Iron ln sol Mang. Iron Mang.

Manganese Concentrates 7. 7 20.85 5.8 4.2 Cleaner Tailing B 21.1 32.85 7.4 16.3 2 Cleaner Tailing 45.7 42.75 10.8 p 5.5 51.3 Talling 25.5 39.30 V 17.4 4.0 26.3

Calculated V q T Heads...- 100.0 38.1 11.4 9.1 100.0

. d H Example N o. 6

This test demonstrates the ,selectivityofthe. 516015515: alcohol derivative reagent of the invention with respect to the carbonates asagainst the oxides.

"An oxide'manganese ore having a-highlime'conteut was used in this test. The ore is known asfcolumbiawManganesej, and is from the Ely District of"Nev a da H The principal mang anesejminerals present are psilomelane and 'manganite',' there being minor quantities. of manganese silicates. Calcite,'CaCO is. the principal gangne con stituent along with quartz. v

In this instanceit was desired "to remove thecalcite prior to the recovery of the manganese minerals. 7 The procedure employed involved two successive flotation operations, each of which represented a series test. The initial operation utilized the alcohol derivativejreagent of the invention described above as made up from Emcol 4150 for selectively floating the lime constituent, namely, thecalcite, from the remainder of the ore pulp. The subsequent flotation operation utilized the' kerosene phosphine reagentfor floating" ofi the'manganese oxide minerals from the gangne constituents remaining from the initial operation. W

The initial procedure for the Reagent (Lb./Ton) Conditioner Rougher Cleaner Sodium Silicate 2 8 fiminutes "Emcol 4150" Phosphine Reagent. Olelc Acid pH Y lift dilutes The subsequent flotation operation for the separation of.

the oxide manganese minerals from associated gangne was carried out on the tailings or pulp residue of the foregoing operation, as follows:'."" T

Reagent Condi- Rougher Cleaner. Cleaner Cleaner (Lb./Ion) tioner -LA B C Sodium Carbon-v V ate 4. 0

10 a -minutes 7 Sodium Silicate (13 Kerosene Phosphine Reagent 3. 5 0. 5 Oleic Acid 4. l 0. 6 pH 9.0

10 minutes Thenet results of the above flotationoperations were as follows:

7 Percent Assay Percent Percent Distribution Product Weight Insol Lime Mang. Lime Mang. T

Lime Coni l centrates--- 27. 1 5. 04 45. 8 3. 25 99. 0 3. 3 Manganese Coucen-' trates 50.4 17.0 0. 2 39.8 0 8 76.4 Tailing 22.5 44.7 0.1 23.7 0 2 20.3

Calculated Head 100. 0 20. 0 12. 5 26. 3 100. 0 100. 0

\ While the "Emcol 4150 alcohol derivative reagent of the invention has been found to be especially useful in the selective flotation of the'carbonates as against the oxides, the amyl alcohol reagent of the invention maybe also em. p yed-ifl In he. srl nian dwe itheirqthi s tendency: of the 'a'myl alcohol must be tak n int sideration. :5; 1

The carbonates are floated oiffirst, 'inasmuch'as the other reagents of the-iiivention are not ordinarilyselective as between the carbonates and oxides.

. A carbonate manganese ore fro m the Caselton properties of CombinediiMetalsiaReductionzfiompanyiin the 'Pioche'Distn'ct of Nevada wasfthe subject ofthistest.

" The principal manganese mineral present in this ore is "have been used, since no problem of selective separation as against oxides exists with this ore.

The procedure was as follows:

Reagent Condi- Rougher Cleaner 'LCIeaner Cleaner -'.(Lb./Ton) rtioner (A B G Sodium Carbon- 4.0 Nothate. ing. Indusoil (mixture 1.2 0. 15

.ofiatty and 1 resin acids). 'Emcol 4150" 0.07 0. 02

Phosphine Re- 5 agent. minutes r .tSodium Silicate--- fin 0.3 0.25 0.25

.minutes The following: results were obtained:

1 'Percent'Assey Percent Product Percent Distribu- Weight tion,

Iron Insol Lime Mang. Mang.

...Manganese Concenmites 75.1 9.4 10.6 9.8 19.9 84.5 Telling 24. 9 935 43. 3 3. 4 1130 15. 5

Gaiculated Heads 100. 9.4 18. 8 a 8.2 "17.7 100. 0

Example N0. 8

The ore was' mangano-sideritedrom the same source and having essentially thesameconstituents as'thatof the immediately preceding 'test. Theamyl alcoholreagent of the invention was employed in this test; however, "in the following manner:

'Reagents '(LbJTon) Cpndi- Rougher "Scavenger Cleaner tioner Sodium Silicate 2.0 -Nothing mAmyLAicoholPhos- 1.0

phine Reagent. Indusoll(mixture of -0. 0525 0. 25

fatty and resin I acids).

5 minutes Sodium Di 0.6

Ghromate.

15 minutes The following results wereobtained:

J Percent Assay 'Percent Product Percent I Distribu- Weight tlon,

, Iron Insol Lime Mang. Mang.

Manganese Concentrates i 54.7 .8.2 9.0 14.4 17.5 81.5 Tailing 45.3 5. 5 54.4 5.4 1 8:; 218.5

Calculated I Head. 100.0 =7.'0 29.6 10.3 1L7 400.0

can be fairly compared' withtherresults "setafo'rthlin-Table 9 on page 14 of the previously referred to U. S. Bureau of Mines Report of Investigations "No."41i 1witlr'respect to the Caselton-sample, since the ores involved came "from" thesameypropertiesand'are "of-corresponding char acter. In this connectionyit should be noted that the grade produced in the: Bureau 'l'Of -Minestesting is noncommercial, while the respective grades of the.foregoing exampleszare definitely: commercial.

Example No. 9

.principalj= gangue" constituent is :quartz, together with small .quantitiessof other silicates. .Sulfide minerals are present .in the form.ofpyrite, sphalerite;v andygalena.

'I'hesulfideminerals werelfloatedofii fromthe orepulp ,in customary-manner. .Thetailingsorpulp residue from that operation were then subjected tothe process .of the invention as follows, this being a series test:

..Beagent.(Lb./Ton) Rougher. Cleaner A Cleaner-B Sodium Carbonate-.-

-S0dium Silicate Nothing.

"Emcol 4150" Phosphlne Reagent.

Olcic Acid 2. 25 Emcol 4150 Phos- 0. 4

phine'Rea-gent I(imaged). V 8 5 p 15 minutes The following results were obtained:

. Percent Assay Percent Product Percent Distribu- Weight .tion,

Insol Mang. Mang.

Manganese Concen-- trates 55.1 8. 6 33. 25 75. 9

-- Calculated fleadsun 100. 1 31. 7 100. 0

.Example No. 10

This .test was :performed onan oxidized zinc 0reobwtained from theiproperty-bf United Minerals'Reserveiin -the- Big-WoodRiver- Region of-1daho. The principal zinc "miner'alsin this ore are'smithsonite' (-ZriCog' and-calamine '(HgZnSiOg) with "smaller 'amounts *of willemite .(Zn SiO Theoxidized lead mineral cerussite (PbCO 'is also present as a principal ore mineral. The gangue is mostly quartz and the feldspars, with smaller quantities of .zircon (.ZnSiO Thecerussite -was:sulfidized, and was then..floated off from-the ore pulp with normal sulfide collectors. The "tailings orpnlp residue "of that operation was then treated inaccordance with the invention, ina seriestest; for the recovery of the'carbonate zinc mineral:

The'resultsof the immediately foregoing two'examples present.

as Tribune Oxide takenfrom the Caselton property of Combined Metals Reduction Company in the Pioche District of Nevada. The principal lead minerals are auglesite ((PsSOQ' and cerussite. Minor quantities of plumbojarosite, PbFe' (OH) ',(SO and galena are also This was a comparative test made on a batch basis, to

The gangue is made tip-mostly of quartz and the feldspars, along with small quantities of iron and manganese oxides and zircon.

I Thefollowing'rsults were obtained?" 1 Percent Assayi; Percent ,7 Product Percent Distri- Weight 5 button,

' Lead Insol v Lead Lead Concentrates 13. 4 2.6 23. 5 57. 0 Lead Cleaner Tailing. 21. 9 10.9 e 47. 2 18. 0 Tailin 04.7 2.9 74.0 r r 25.0

Calculated Head 100.0 a, 7.3 g 62.4 100.0

In comparing the results of the respective tests, it should be noted that the grade of lead concentrates is comparable, but that there was a considerably greater :loss

' (over three times as great) of lead inthe tailings of the conventional process, aswagainst the process of theinvention. 1

Example No. 12]. 1 The subject of this test was a calcium tungstate ore known as Minerva Chief from the Mount Wheeler District of Nevada. The valued mineral in that ore is scheelite (CaWO .and the gangue is mostly quartzand calcite.

The process of the invention was applied in the following manner, this being a series test: v

show the difference between standard sulfidization meth- Reagents (LbJTon) BallMlll Rougher Cleaner ods as against the process of the invention.

The ore was treated in accordance with the invention, Sodium Carbonate 4. as follows. Sodium Silicate 1.

- Quebracho 5 0.1

Emeol 4150" Phosphin Reagent. V 0. 5 0. 034 0. 01 c1 'Olei' and 20 minutes 0 081 o 002 8811618 9 Reagent Ball Con- Rougher 15 minutes (Lb/Ton) Mill ditioner V V 5 A B The concentrate was cleaned three times, and the following results were obtained: Sodium Carbom 4.0 Nothing K e Pho 3, 2 4, 3 Product Percent Percent Percent 1 hine Reagent. Weight Assay Distribution So dium Silicate 2 5 minutes W0; W0; Indusnil 2,5 0.25 40 Concentrate 1.35 49.4 82.05 In 3.3 Telling 98.65 0.15 17.95

5 15 minutes minutes Calculated Head 100.0 0.81 100.00

Example N0. 13 a The followmg results were obtamed'. 7 Another typeof calcium tungs'tate ore from the ro a P erty of Midwest Development, Inc. in the Delta District 7 V of Utah was treated by this test. Like the ore 'of the Product Pemnt Percent Assay g gfg immediately: preceding example, the valued mineral ore Weight bution, is scheelite. The gaugue is made up largely of garnet Lead Insol ead and quartz V a I This was a batch test carried out in the following Lead Concentrates 17. 7 23. 1 13.6 66. 1 manner.

' Lead Cleaner Tailtng B- 14.4 4. 0 42. 2 11. 1

Lead Cleaner Tailing A- 27.6 3.3 64.2 14.7

Taflmg Reageuts(Lb./Ton)' Ball M111 Rongher Cleaner Calculating Heads 100.0 0. 2 60. 5 100. 0

Sodium Carbonate 3.0 I godium ssllllfcatten.--

V opper u ae..- .15

' The standard sulfidlzation and sulfide flotatronwere gudelbmcln ian M2 v 0 um yan 8 carr ed out as follows. fl iz Phosphme 0 1 0 024 eagen v V Oleio Acid. 0. 3 15 in 0667 0. 12 Bea ent Lb. Ton BallMlll Lead Oxide Lead es g I Rougher Rougher pH Sagan: glm r de u 2-8 Y The concentrate was cleaned three times, and the folmm 2 lowin results were obtained- Thiocarbanalid 0.3 g a Aergflgat 242 (thlophos- 0.05 0.1

p a e Product Percent Percent Percent 506mm silicate M p e t Assay Distribution Potassium Amyl Xanthate- 0. 2

Potassium EthylXanthate- 0.1 0.3 a I v W0a W0a Rggfig2fi Concentrates 0.79 .316 64;71 Cleveland dun-#2 (Hard- 0.1 0.3 8:233; @fifigf and o 3-53 dCreosote). a

mmmutes Talltug 90.91 0. 024 e23 swim Concentrates..---' 100.00 0.40 100.00

eaesasat'ss The ore treated, was amanganesetnngstate known as Deer Trail from the'Mount-tlihee'alerDistrict: of Nevada.

'Y'Ehe valued mineral .ishiibnerite .(MHWO4) ,ttheifgangue being principally quartz, with smaller amounts of iron oxide and garnet.

The process of the invention was applied in a batch test, as follows:

Reagents (LbJTon) Rougher Quebracho Kerosene Phosphine Reagent lc Acid Emcol 4150" Ph hine Reagent Sodium Oleate Emcol X-25 (Sulfonated 8 to 10 carbon alcohol) The following results were obtained:

The above tests all involve ores of metallic or submetallic character. The invention is not restricted to ores of such character, however, but is also applicable to the recovery of various non-metallic minerals. The following example is concerned with the application of the invention to a fluoritic ore for the recovery of the non-metallic mineral fluorite (CaF Example No. 15

The fluoritic ore treated was from the Mount Wheeler District of Nevada, being known as Williams Fluorite. This ore is composed principally of the mineral fluorite, the gangue constituents being quartz and calcite. This was a batch test carried out as follows:

Reagent (Lb./Ton) Ball Mill Rougher Cleaner A Cleaner B Sodium Carbonate..- 4.0 Nothing. Sodium Silicate 1.0 Copper Sulfate 0. 5 Quebracho 0. 5 "Emcol 4150" Phosphine Reagent 0.3 0. 9 0.2

minutes Olelc Acid 2. 1 0. 6

10 minutes The following results were obtained:

Percent Assay Percent Percent Distri- Product Weight bution,

08F: Total S102 CBFz Lime Concentrates 51. 2 98. 95 71. 5 0. 46 67. 3 Cleaner Tailiug B. 6. 5 95. 81 70. 1 1. 36 8. 3 Cleaner Talling A- 14. 3 86. 89 63. 2 6. 72 16. 5 Tailing 28. 0 21. 25 16. 2 70. 5 7. 9 Calculated Head 100. 0 75. 27 100. 0

The foregoing examples are typical of the application of the process of the invention to naturally occurring ores -:14 -which are *ordinarilymot susceptible" to satisfactory flota- F tion onthe basis of sulfidization md of 'collection'- v. ith

those I collectors normally used insiilfide' flotation.

These examples indicate how the reagents of the-in- 5 -vention may =bee employed. in a variety of =situations to effect recovery of valuable rr'iineral' constituents of amore pulp. It should be borne in mind, however, that the process ofthednventiomis best applied -in" keeping with knowledge or a. general'rcharacter avalilable and commonly i '10 -used-in the-art of flotation with respect. to specialproblems presented by particular ores. "Thus, the specific tests' here presented should be regarded, in their details, as merely illustrative.

While certain of the reagents which conform to the 15 inventive class here set forth are old in themselves as chemical compositions, it is believed that others are unique. These latter are, therefore, claimed in and of themselves herein as new compositions of matter.

Whereas this invention is here specifically described with respect to particular procedural steps and particular reagents, it is to be understood that various other practices and forms are possible within the generic concepts disclosed, and are contemplated as being within the scope of the claims which here follow.

I claim:

1. A process of concentrating ores by selective froth flotation, comprising subjecting an ore pulp to a froth flotation operation in the presence of a reagent selected from the group consisting of a hydride of phosphorous and an organic phosphine.

2. The process recited in claim 1, wherein a nonsulphydric collector reagent is present in the said flotation operation.

3. The process recited in claim 2, wherein the ore pulp embodies a mineral selected from the group consisting of an oxidized type of metallic character, an oxidized type of submetallic character, and a non-metallic type, as the value to be recovered, and the collector reagent is carboxylic in character.

4. A process of concentrating ores by selective froth flotation, comprising subjecting an ore pulp to a conditioning operation in the presence of a reagent selected from the group consisting of a hydride of phosphorous and an organic phosphine, and thereafter subjecting the so-conditioned ore pulp to a froth flotation operation in the presence of a non-sulphydric collector reagent.

5. A process of diiferential froth flotation, comprising subjecting an ore pulp containing an iron mineral, exclusive of iron sulfide, and at least one valued mineral,

to a froth flotation operation in the presence of a reagent selected from the group consisting of a hydride of phosphorous and an organic phosphine, as a depressant for the said iron mineral, and in the presence of a collector reagent for the said valued mineral.

6. The process recited in claim 5, wherein the ore pulp is conditioned with the said depressant reagent prior to the froth flotation operation.

7. A process of differential froth flotation, comprising subjecting an ore pulp containing a carbonate mineral and an oxide mineral to a froth flotation operation in the presence of a reagent prepared by intermixing a hydride of phosphorous with an aqueous solution of an organic liquid selected from the group consisting of an alcohol and an ester of an alcohol, and in the presence of a nonsulphydric collector; recovering a float product made up of the carbonate mineral; subjecting the sink product from said flotation operation to a re-flotation operation in the presence of a reagent (other than the said reagent) selected from the group consisting of a hydride of phosphorous and an organic phosphine carried by a hydrocarbon vehicle, and in the presence of a non-sulphydric collector; and recovering a float product made up of the oxide mineral.

8. The process of producing a flotation reagent, comf 15 i #16 prising pouring upon a body of waterin an open vessel 2,242,224 Bley; .Q..; May 20, 1941 into said body of Water; and permitting the phosphine a quantity of a liquidhydrocarbon lighter than water; 2,584,112 Brown Feb. 5,1952 introducing a quantity of an alkaline-earth phosphide r v I OREIGN, PATENTS gas evolved by hydrolysis to pass through and beabsorbed 5 899,640 2 G r 1y'8 1949 by the, said liquid hydrocarbon. I i I k References Cited in the file of this patent UNITED STATES PATENTS 2,132,902 Lenher Oct. 11, 193s in 

7. A PROCESS OF DIFFERENTIAL FROTH FLOTATION, COMPRISING SUBJECTING AN ORE PULP CONTAINING A CARBONATE MINERAL AND AN OXIDE MINERAL TO A FROTH FLOTATION OPERATION IN THE PRESENCE OF REAGENT PREPARED BY INTERMIXING A HYDRIDE OF PROSPHOROUS WITH AN AQUEOUS SOLUTION OF AN ORGANIC LIQUID SELECTED FROM THE GROUP CONSISTING OF AN ALCOHOL AND AN ESTER OF AN ALCOHOL, AND IN THE PRESENCE OF A NONSULPHYDRIC COLLECTOR; RECOVERING A FLOAT PRODUCT MADE UP OF SAID CARBONATE MINERAL; SUBJECTING THE SINK PRODUCT FROM SAID FLOTATION OPERATION TO A RE-FLOTATION OPERATION IN THE PRESENCE OF A REAGENT (OTHER THAN THE SAID REAGENT) SELECTED FROM THE GROUP CONSISTING OF A HYDRIDE OF PHOSPHOROUS AND AN ORGANIC PHOSPHINE CARRIED BY A HYDROCARBON VEHICLE, AND THE PRESENCE OF A NON-SULPHYDRIC COLLECTOR; AND RECOVERING A FLOAT PRODUCT MADE UP OF THE OXIDE MINERAL. 